Treatment of calcium carbonate containing materials for increased filler load in paper

ABSTRACT

The present invention concerns a process for preparing self-binding pigment particles from an aqueous suspension of calcium carbonate containing material, wherein an anionic binder and at least one cationic polymer are mixed with the suspension.

CROSS-REFERENCE TO RELATED APPLICATIONS

This is a continuation of U.S. application Ser. No. 14/396,148, filedOct. 22, 2014, which is the U.S. National phase of PCT Application No.PCT/EP2013/059197, filed May 2, 2013, which claims priority to EuropeanApplication No. EP12167650.6, filed May 11, 2012 and U.S. ProvisionalApplication No. 61/648,642, filed May 18, 2012, the contents of whichare hereby incorporated by reference.

The invention relates to a process for preparing self-binding pigmentparticles, to a self-binding pigment particle suspension as well as to apaper product comprising self-binding pigment particles and to the useof the self-binding pigment particle suspension.

Mineral materials and binders are among the main constituents used inthe manufacture of numerous products such as paints, paper and plasticmaterials. Therein, mineral materials contribute mechanical and opticalproperties, while the binder, generally latex-based and in the form ofaqueous suspensions or dispersions, provide the necessary adhesion andcohesion for the respective constituents of the end product to beproduced.

In order to avoid the logistic difficulties of handling mineralmaterials and binders separately, and further to avoid the unwantedphysical and chemical interactions developed in comparable mixtures ofmineral materials and binders, self-binding pigment particles have beendeveloped and are known to industry. In this regard, self-bindingpigment particles having both the properties of the mineral material andof the binder may be directly implemented in a variety of applications.This unique product named self-binding pigment particles refers todistinct, solid particles, formed of mineral material and binder thatare intimately bound to one another. The internal cohesion forces aresuch as to provide the self-binding pigment particles with excellentmechanical stability.

Self-binding pigment particles can be produced from calcium carbonatecontaining mineral materials, for example, from natural mineral pigmentmaterials which are commonly prepared by a process implementing at leastone step of grinding mineral materials in the presence of binder.Grinding refers to an operation leading to a reduction in the particlesize, i.e. the mineral materials in the self-binding pigment particleshave a smaller diameter than the initial mineral material used toproduce them. Such self-binding pigment particles are described in anumber of documents, including WO 2006/008657, WO 2006/128814, and WO2008/139292.

For completeness, the Applicant would like to mention the followingapplications in its name, which also refer to processes for preparingself-binding pigment particles: unpublished European Patent Applicationswith filing numbers 11 160 900.4, 11 160 926.9, 11 179 604.1, and 11 179572.0.

The processes for preparing self-binding mineral pigment particles knownin the art are often limited to the preparation or the co-grinding ofsuspensions having a low solids content. However, the preparation of lowsolids content suspensions has the disadvantage that the obtainedgrinding product has to be concentrated before being shipped to otherfacilities for further processing. During the time and energy consumingconcentrating step, very often an undesired loss of polymeric binder isobserved, and, additionally, unwanted agglomerates are formed.Furthermore, the prior art processes often lead to a suspension having ahigh total organic content of the aqueous phase of the groundsuspension. Moreover, the addition of dispersant, however, inter aliaaffects the adsorption of the binder to the particles duringco-grinding.

Self-binding pigment particles containing binders that are based onpolymers which are derived from natural or renewable resources are aparticular point of interest for environmental reasons. However, suchself-binding pigment particles are often formed from negatively chargedmodified polysaccharides, which may be unfavorable for some fields ofapplications. For example, due to their negative surface charge suchpigment particles are difficult to retain during paper productionprocesses. This leads to a high consumption of self-binding pigmentparticles and additional retention aid during paper production to obtainthe desired filler load in the paper.

A further problem, which very often has significant impact on themechanical and optical properties of papers and paper coatings made fromsuch self-binding pigment particles, is encountered in respect to thebinding between the fibres and such self-binding pigment particles. Theself-binding pigment particle suspensions often diminish the mechanicaland optical properties of the corresponding end products. One reason forthis may be the shape of the self-binding pigment particles, which couldhamper the interaction between the self-binding pigment particles andthe fibres of the paper. Thus, to produce paper articles withwell-adjusted mechanical and optical properties, the interactionboundaries between the self-binding pigment particles and the fibres inthe paper have to be optimized.

Furthermore, high filler levels in paper are desirable since these wouldprovide the possibility to reduce the amount of wood fibers in thepaper. Moreover, papers with high filler content will dry faster, and,as a result, the paper machine can run faster. Consequently, theaddition of high levels of filler can reduce paper production costs andcan save natural resources. However, such high filler levels oftenreduce the area of contact between the remaining fibres. As a result,retaining high amounts of filler with a suboptimal shape produces aweaker sheet that can break more easily on the paper machines, sizepresses, coaters, winders, printing presses, printing machines, or copymachines.

U.S. Pat. No. 5,611,890 relates to a strong, soft filled tissue papercomprising a non-cellulosic particulate filler, wherein said fillercomprises 5 to 50 wt.-% of said tissue paper. WO 03/087472 discloses afiller treatment comprising the preparation of swollen starch-latexcompositions, and the addition of said compositions to a fillersuspension. The use of these treated fillers during papermaking improvesfiller retention and produces filled papers, where addition of thefiller has only a minimal negative effect on strength properties. Apapermaking filler material which has been surface treated with acationic polymer is described in CA 2,037,525. The article “Improvementof paper properties using starch-modified precipitated calcium carbonatefiller” of Zhao et al., TAPPI Journal 2005, vol. 4(2), is concerned withcommercial precipitated calcium carbonate fillers that have beenmodified with corn and potato raw starches. These modified fillers wereused as papermaking fillers to improve the strength in high fillercontent papers.

In view of the foregoing, improving the self-binding pigment particleproduction process remains of interest to the skilled man. It would beespecially desirable to provide a process for making self-bindingmineral pigment particles, wherein the mineral pigment particles do nothave to be co-ground with the binder since milling is a very cost- andtime-consuming step. Furthermore, the particle structure of the mineralpigment particles can change during milling and, therefore, thecharacteristics of the mineral pigment particles may be different aftermilling. Additionally, it would also be desirable to provide a processfor making self-binding pigment particles, which can be applied tomineral pigment suspensions having a high solids content, thus, avoidingan energy and time consuming concentrating step and, e.g., the formationof significant amounts of unwanted agglomerates. Furthermore, it wouldbe desirable to provide self-binding pigment particles that improve thebinding between the fibres in papers and paper coatings and theself-binding mineral pigment particles, and, thus, allows for theproduction of paper articles with well-adjusted mechanical and opticalproperties. In particular, it is desirable, to provide a process formaking self-binding pigment particles, which allow for the provision ofa filler material that shows a good retention in paper productionprocesses, and avoids the use of large amounts of retention aids.

The foregoing and other objectives are solved by the subject-matter asdefined herein in the independent claims.

According to one aspect of the present invention, a process forpreparing self-binding pigment particles is provided, the processcomprising the following steps:

a) providing an aqueous suspension comprising at least one calciumcarbonate containing material,

b) providing at least one acid or acid salt, wherein the anion of theacid or acid salt is capable of forming water-insoluble calcium salts,

c) providing an anionic polymeric binder, wherein said binder comprisesat least one modified polysaccharide,

d) providing at least one cationic polymer,

e) mixing the aqueous suspension of step a) with the at least one acidor acid salt of step b), and

f) mixing the suspension of step e), the anionic polymeric binder ofstep c) and the at least one cationic polymer of step d).

According to another aspect, the present invention refers to aself-binding pigment particle suspension which is obtainable by theprocess according to the present invention.

Another aspect of the present invention refers to the use of theinventive self-binding pigment particle suspension in paper, plastics,paint, coatings, concrete and/or agricultural applications.

Still another aspect of the present invention refers to a paper productcomprising the self-binding pigment particles, wherein the particles areat least partially coated with a water-insoluble calcium salt formedfrom an acid or acid salt, an anionic binder comprising at least onemodified polysaccharide, and at least one cationic polymer.

Advantageous embodiments of the inventive method are defined in thecorresponding sub-claims.

According to one embodiment in step f) of the inventive process, thesuspension obtained by step e) is, in a first step, mixed with theanionic polymeric binder of step c), and then, in a second step, ismixed with the at least one cationic polymer of step d). According toanother embodiment in step f) of the inventive process the suspensionobtained by step e) is mixed with the anionic polymeric binder of stepc) and the at least one cationic polymer of step d) in one step.According to still another embodiment in step f) of the inventiveprocess, the suspension obtained by step e) is, in a first step, mixedwith the at least one cationic polymer of step d), and then, in a secondstep, is mixed with the anionic polymeric binder of step c).

According to one embodiment the suspension obtained by step e) isconcentrated before step f). The concentration step can be carried outby using thermal and/or mechanical methods well known to the skilledperson.

According to one embodiment the at least one calcium carbonatecontaining material is selected from calcium carbonate, calciumcarbonate containing minerals, mixed calcium carbonate based fillers, ormixtures thereof, preferably the calcium carbonate containing materialis calcium carbonate, more preferably precipitated calcium carbonate(PCC) and, most preferably is scalenohedral PCC (S-PCC), rhombohedralPCC (R-PCC), prismatic PCC (P-PCC), cubic PCC (C-PCC), or a mixturethereof. According to another embodiment the at least one calciumcarbonate containing material of step a) is provided in form ofparticles having a weight median particle diameter d₅₀ value from 0.1 to100 μm, preferably from 0.2 to 50 μm, more preferably from 0.5 to 25 μm,and most preferably from 1.0 to 10 μm. According to still anotherembodiment the at least one calcium carbonate containing material ofstep a) is provided in form of particles having a specific surface areafrom 0.1 to 200 m²/g, preferably from 0.5 to 100 m²/g, more preferablyfrom 1.0 to 50 m²/g, and most preferably from 2.0 to 10 m²/g.

According to one embodiment the aqueous suspension of step a) has asolid content from 1 to 99 wt.-%, preferably from 15 to 70 wt.-%, morepreferably from 10 to 50 wt.-%, and most preferably from 12 to 40 wt.-%,based on the total weight of the suspension. According to anotherembodiment the suspension of step a) comprises further minerals such as,talc, kaolin, Ti0₂, bentonite and mixtures thereof.

According to one embodiment the at least one acid or acid salt of stepb) is added in an amount from 0.001 to 40 wt.-%, preferably from 0.005to 20 wt.-%, more preferably from 0.01 to 10 wt.-%, and most preferablyfrom 0.05 to 5 wt.-%, based on the total weight of the dry calciumcarbonate containing material. According to another embodiment the atleast one acid or acid salt of step b) is selected from the groupcomprising citric acid, oxalic acid, phosphoric acid, sulphuric acid,arsenic acid and iodic acid or salts thereof, and mixtures thereof.

According to one embodiment the suspension obtained by step e) has asolid content from 2 to 99 wt.-%, preferably from 10 to 60 wt.-%, morepreferably from 15 to 45 wt.-%, and most preferably from 20 to 30 wt.-%,based on the total weight of the suspension.

According to one embodiment the at least one modified polysaccharide isa carboxymethyl derivate and/or a carboxymethyl hydroxypropyl derivateand/or a carboxymethyl hydroxyethyl derivate of a polysaccharide,preferably a carboxymethylcellulose, an anionic guar, an anionic starch,or xanthan gum. According to another embodiment the at least onemodified polysaccharide has a degree of substitution of the hydroxylgroups in the range from 0.4 to 2.0, preferably from 0.5 to 1.8, morepreferably from 0.6 to 1.6, and most preferably from 0.7 to 1.5.

According to still another embodiment the intrinsic viscosity of the atleast one modified polysaccharide is in the range from 5 to 500 ml/g,preferably from 10 to 450 ml/g, more preferably from 50 to 350 ml/g, andmost preferably from 100 to 200 ml/g.

According to one embodiment the binder of step c) is in form of anaqueous solution or dry material, preferably in form of a solutionhaving a binder concentration from 1 to 70 wt.-%, preferably from 2 to55 wt.-%, more preferably from 5 to 50 wt.-%, and most preferably from30 to 50 wt.-%, based on the total weight of the solution. According toanother embodiment the binder of step c) is added in an amount from0.001 to 20 wt.-%, preferably from 0.005 to 15 wt.-%, more preferablyfrom 0.01 to 10 wt.-%, and most preferably from 0.05 to 5 wt.-%, basedon the total weight of the dry calcium carbonate containing material.

According to one embodiment the at least one cationic polymer of step d)is selected from the group comprising polyethyleneimines,polyacrylamides, cationic epichlorohydrin resins, cationic starch,cationic guar, and mixtures thereof. According to still anotherembodiment the at least one cationic polymer of step d) is in form of asolution or dry material, preferably in form of a solution having aconcentration from 0.5 to 70 wt.-%, preferably from 1 to 25 wt.-%, morepreferably from 1.5 to 20 wt.-%, and most preferably from 2 to 10 wt.-%,based on the total weight of the solution. According to still anotherembodiment the at least one cationic polymer of step d) is added in anamount from 0.001 to 20 wt.-%, preferably from 0.005 to 15 wt.-%, morepreferably from 0.01 to 10 wt.-%, and most preferably from 0.05 to 5wt.-%, based on the total weight of the dry calcium carbonate containingmaterial.

According to one embodiment the self-binding pigment particle suspensionis used in wet end process of a paper machine, in cigarette paper,board, and/or coating applications, or as a support for rotogravureand/or offset and/or ink jet printing and/or continuous ink jet printingand/or flexography and/or electrophotography and/or decoration surfaces.According to another embodiment the self-binding pigment particlesuspension is used to reduce sun light and UV exposure of plant leaves.

According to one embodiment the inventive paper product has a highertensile index compared to a paper product, wherein the inventiveself-binding pigment particles are replaced by the same amount ofcalcium carbonate containing material particles, preferably the tensileindex is at least 5% higher, more preferably at least 7% higher, andmost preferably at least 10% higher compared to the tensile index of apaper product, wherein the inventive self-binding pigment particles arereplaced by the same amount of calcium carbonate containing materialparticles.

It should be understood that for the purpose of the present invention,the following terms have the following meaning:

A “suspension” or “slurry” in the meaning of the present inventioncomprises insoluble solids and water, and optionally further additives,and usually contains large amounts of solids and, thus, is more viscousand can be of higher density than the liquid from which it is formed.

A “calcium carbonate containing material” in the meaning of the presentinvention can be a mineral material or a synthetic material having acontent of calcium carbonate of at least 50 wt.-%, preferably 75 wt.-%,more preferably 90 wt.-%, and most preferably 95 wt.-%, based on thetotal weight of the calcium carbonate containing material. The term “drycalcium carbonate containing material” is understood to refer to calciumcarbonate containing material particles having a total surface moisturecontent of less than 0.5 wt.-%, preferably less than 0.2 wt.-% and morepreferably less than 0.1 wt.-%, based on the total weight of theparticles.

“Ground calcium carbonate” (GCC) in the meaning of the present inventionis a calcium carbonate obtained from natural sources, such as limestone,marble, calcite or chalk, and processed through a wet and/or drytreatment such as grinding, screening and/or fractionation, for exampleby a cyclone or classifier.

“Precipitated calcium carbonate” (PCC) in the meaning of the presentinvention is a synthesized material, generally obtained by precipitationfollowing a reaction of carbon dioxide and calcium hydroxide (hydratedlime) in an aqueous environment or by precipitation of a calcium and acarbonate source in water. Additionally, precipitated calcium carbonatecan also be the product of introducing calcium and carbonate salts,calcium chloride and sodium carbonate for example, in an aqueousenvironment.

An “acid” in the meaning of the present invention is defined as aBrønsted-Lowry acid, that is to say, it is an H₃O⁺-ion provider. An“acid anion” is defined as a deprotonated form of a H₃O⁺-ion provider,i.e. it is a conjugated base of an acid. An “acid salt” is defined as anH₃O⁺-ion provider that is at least partially neutralised by anon-hydrogen cation. A “salt” is defined as an electrically neutralionic compound formed of anions and non-hydrogen cations. A “salt” maycomprise the anhydrous form as well as forms comprising crystal water(hydrate).

For the purpose of the present application, “water-insoluble” materialsare defined as materials which require more than 100 ml of water pergram material for dissolving the material at 20° C. as defined by theEuropean Pharmacopoeia. Preferably the materials are dissolved at a pHfrom 7.5 to 14.

An “anionic polymeric binder” in the meaning of the present invention isdefined as a polymer that is capable of binding to the surface of thecalcium carbonate containing material and to itself and/or to certainother materials upon drying. The binding includes ionic interactionsand/or hydrogen-hydrogen-bridge bonds between the groups on the surfaceof the calcium carbonate containing material particles and thefunctional groups of the polymer. Furthermore, the term “anionicpolymer” or “anionic polymeric binder” in the meaning of the presentinvention refers to a polymer having a negative net charge. Saidcompound is typically modified with anionic groups. The term “anionic”does not exclude the presence of cationic groups provided that the sumof individual charges is negative.

The term “cationic polymer” in the meaning of the present inventionrefers to a polymer having a net positive charge. Said compound istypically modified with cationic groups. The term “cationic” does notexclude the presence of anionic groups provided that the sum ofindividual charges is positive.

The “particle size” of the calcium carbonate containing material in themeaning of the present invention is defined by its distribution ofparticle sizes. The value d_(x) represents the diameter relative towhich x % by weight of the particles have diameters less than d_(x).This means that the d₂₀ value is the particle size at which 20 wt.-% ofall particles are smaller, and the d₇₅ value is the particle size atwhich 75 wt.-% of all particles are smaller. The d₅₀ value is thus theweight median particle size, i.e. 50 wt.-% of all grains are bigger orsmaller than this particle size. For the purpose of the presentinvention the particle size is specified as weight median particle sized₅₀ unless indicated otherwise. For determining the weight medianparticle size d₅₀ value for particles having a d₅₀ value from 0.2 and 5μm, a Sedigraph 5120 device from the company Micromeritics, USA, can beused.

A “specific BET surface area” (SSA) in the meaning of the presentinvention is defined as the surface area of the mineral pigment dividedby the mass of the mineral pigment. As used herein, the specific surfacearea is measured by nitrogen adsorption using the BET isotherm (ISO9277:2010) and is specified in m²/g.

For the purposes of the present invention, the term “viscosity” withreference to coating formulations, refers to Brookfield viscosity. TheBrookfield viscosity may be measured by a Brookfield viscometer at 23°C. at 100 rpm and is specified in mPa·s.

The term “intrinsic viscosity” as used in the context of the presentinvention is a measure of the capability of a polymer in solution toenhance the viscosity of the solution and is specified in ml/g.

The term “degree of substitution” as used in the context of the presentinvention is specified in respect to the total amount of substituted ormodified groups per unmodified monomer unit of the originalpolysaccharide.

“Modified polysaccharides” in the meaning of the present invention arepolysaccharides, wherein at least a part of the hydroxyl groups iscarboxylated. Additionally, the modified polysaccharides may containother modifications such as aldehyde groups.

Where the term “comprising” is used in the present description andclaims, it does not exclude other elements. For the purposes of thepresent invention, the term “consisting of” is considered to be apreferred embodiment of the term “comprising of”. If hereinafter a groupis defined to comprise at least a certain number of embodiments, this isalso to be understood to disclose a group, which preferably consistsonly of these embodiments.

Where an indefinite or definite article is used when referring to asingular noun, e.g. “a”, “an” or “the”, this includes a plural of thatnoun unless something else is specifically stated.

Terms like “obtainable” or “definable” and “obtained” or “defined” areused interchangeably. This, e.g., means that, unless the context clearlydictates otherwise, the term “obtained” does not mean to indicate that,e.g., an embodiment must be obtained by, e.g., the sequence of stepsfollowing the term “obtained” even though such a limited understandingis always included by the terms “obtained” or “defined” as a preferredembodiment.

The inventive process for preparing self-binding pigment particlesprovides several advantages. Firstly, the inventive process provides agood adsorption of the binder to the particle surface and, thus, noadditional co-grinding step of the calcium carbonate containing materialtogether with the binder has to be performed. Secondly, the self-bindingmineral pigment particles obtained by the inventive process show animproved binding to fibres in paper product processes and, therefore,the filler loaded in the paper can be increased while maintaining themechanical strength properties of the paper. Additionally, the formationof unwanted aggregates is reduced by applying the inventive processsince a subsequent concentrating step can be avoided due to theprocessing of a high solids content suspension as set out above.

In the following the details and preferred embodiments of the inventiveprocess will be set out in more detail. It is to be understood thatthese technical details and embodiments also apply to the inventiveself-binding pigment particle suspensions and their use.

Step a)

In step a) of the process according to the present invention an aqueoussuspension comprising at least one calcium carbonate containing materialis provided. According to one embodiment of the present invention, theaqueous suspension is obtained by mixing particles of the calciumcarbonate containing material with water.

The calcium carbonate containing material can be selected from calciumcarbonate, calcium carbonate containing minerals, mixed carbonate basedfiller, or mixtures thereof.

According to one embodiment of the present invention, the calciumcarbonate containing material is a calcium carbonate. Calcium carbonatemay be selected from ground calcium carbonate and/or precipitatedcalcium carbonate.

Ground (or natural) calcium carbonate (GCC) is understood to be anaturally occurring form of calcium carbonate, mined from sedimentaryrocks such as limestone or chalk, or from metamorphic marble rocks.Calcium carbonate is known to exist as three types of crystalpolymorphs: calcite, aragonite and vaterite. Calcite, the most commoncrystal polymorph, is considered to be the most stable crystal form ofcalcium carbonate. Less common is aragonite, which has a discrete orclustered needle orthorhombic crystal structure. Vaterite is the rarestcalcium carbonate polymorph and is generally unstable. Ground calciumcarbonate is almost exclusively of the calcitic polymorph, which is saidto be trigonal-rhombohedral and represents the most stable of thecalcium carbonate polymorphs. The term “source” of the calcium carbonatein the meaning of the present application refers to the naturallyoccurring mineral material from which the calcium carbonate is obtained.The source of the calcium carbonate may comprise further naturallyoccurring components such as magnesium carbonate, alumino silicate etc.

According to one embodiment of the present invention the GCC is obtainedby dry grinding. According to another embodiment of the presentinvention the GCC is obtained by wet grinding and subsequent drying.

In general, the grinding step can be carried out with any conventionalgrinding device, for example, under conditions such that refinementpredominantly results from impacts with a secondary body, i.e. in one ormore of: a ball mill, a rod mill, a vibrating mill, a roll crusher, acentrifugal impact mill, a vertical bead mill, an attrition mill, a pinmill, a hammer mill, a pulveriser, a shredder, a de-clumper, a knifecutter, or other such equipment known to the skilled man. In casecalcium carbonate containing mineral powder comprises a wet groundcalcium carbonate containing mineral material, the grinding step may beperformed under conditions such that autogenous grinding takes placeand/or by horizontal ball milling, and/or other such processes known tothe skilled man. The wet processed ground calcium carbonate containingmineral material thus obtained may be washed and dewatered by well knownprocesses, e.g. by flocculation, filtration or forced evaporation priorto drying. The subsequent step of drying may be carried out in a singlestep such as spray drying, or in at least two steps. It is also commonthat such a mineral material undergoes a beneficiation step (such as aflotation, bleaching or magnetic separation step) to remove impurities.

According to one embodiment of the present invention the source ofground calcium carbonate (GCC) is selected from marble, chalk, calcite,dolomite, limestone, or mixtures thereof. Preferably, the source ofground calcium carbonate is selected from marble.

According to one embodiment, the suspension of process step a) comprisesone ground calcium carbonate. According to another embodiment of thepresent invention, the suspension of process step a) comprises a mixtureof two or more ground calcium carbonates selected from different sourcesof ground calcium carbonate. For example, the suspension of at least oneground calcium carbonate may comprise one GCC selected from dolomite andone GCC selected from marble.

According to one embodiment of the present invention, the suspension ofprocess step a) consists of at least one ground calcium carbonate. Thesuspension of process step a) may consists of one ground calciumcarbonate, or may consists of two or more ground calcium carbonatesselected from different sources of ground calcium carbonate.

“Precipitated calcium carbonate” (PCC) in the meaning of the presentinvention is a synthesized material, generally obtained by precipitationfollowing reaction of carbon dioxide and lime in an aqueous environmentor by precipitation of a calcium and carbonate ion source in water or byprecipitation of calcium and carbonate ions, for example from CaCl₂ andNa₂CO₃, out of solution. Precipitated calcium carbonate exists in threeprimary crystalline forms: calcite, aragonite and vaterite, and thereare many different polymorphs (crystal habits) for each of thesecrystalline forms. Calcite has a trigonal structure with typical crystalhabits such as scalenohedral (S-PCC), rhombohedral (R-PCC), hexagonalprismatic, pinacoidal, colloidal (C-PCC), cubic, and prismatic (P-PCC).Aragonite is an orthorhombic structure with typical crystal habits oftwinned hexagonal prismatic crystals, as well as a diverse assortment ofthin elongated prismatic, curved bladed, steep pyramidal, chisel shapedcrystals, branching tree, and coral or worm-like form.

According to a preferred embodiment of the present invention, thecalcium carbonate containing material is precipitated calcium carbonate(PCC).

Precipitated calcium carbonate may possess further advantages comparedto ground calcium carbonate. For example, contrary to ground calciumcarbonate, which is mined from large natural deposits of ore, the PCCparticles are prepared synthetically and, therefore, the size and theparticle size distribution can be adjusted during preparing.Furthermore, depending on the reaction conditions the shape andcrystallinity of the PCC particles can be adjusted. Additionally, PCCmineral pigment particles are not contaminated with impurities and,therefore, may show a better brightness compared to GCC.

Another advantage of PCC is the fact that PCC particles typically havemany tips on their outer surface, and thus, are relatively rough. It isbelieved that these tips of the PPC particles can interlock with paperfibres, resulting in an improved binding between the particles and thefibres. Therefore, the use of PCC as filler in paper application maycontrol the paper structure more optimally, and thus, can improve themechanical properties of the paper.

According to one embodiment, the suspension of process step a) comprisesone precipitated calcium carbonate. According to a preferred embodimentof the present invention, the precipitated calcium carbonate comprisesscalenohedral precipitated calcium carbonate (S-PCC).

According to another embodiment of the present invention, the suspensionof process step a) comprises a mixture of two or more precipitatedcalcium carbonates selected from different sources of precipitatedcalcium carbonate. For example, the suspension of at least oneprecipitated calcium carbonate may comprise one PCC selected from S-PCCand one PCC selected from R-PCC.

According to another preferred embodiment of the present invention, thesuspension of process step a) consists of at least one precipitatedcalcium carbonate. The suspension of step a) may consist of one type ofPCC, or may consist of a mixture of two or more types of PCC.

According to one embodiment of the present invention, thecalcium-carbonate containing minerals comprise dolomite.

According to one embodiment, the mixed carbonate based fillers areselected from calcium associated with magnesium and analogues orderivatives, various matter such as clay or talc or analogues orderivatives, and mixtures of these fillers, such as, for example,talc-calcium carbonate or calcium carbonate-kaolin mixtures, or mixturesof natural calcium carbonate with aluminium hydroxide, mica or withsynthetic or natural fibers or co-structures of minerals such astalc-calcium carbonate or talc-titanium dioxide or calciumcarbonate-titanium dioxide co-structures.

According to another embodiment of the present invention the aqueoussuspension comprising the at least one calcium carbonate containingmaterial comprises a further mineral such as talc, kaolin, TiO₂,bentonite, or mixtures thereof.

According to a preferred embodiment of the present invention, the atleast one calcium carbonate containing material is provided in form ofparticles having a weight median particle diameter d₅₀ from 0.1 to 100μm, preferably from 0.2 to 50 μm, more preferably from 0.5 to 25 μm, andmost preferably from 1.0 to 10 μm.

According to a preferred embodiment of the present invention, the atleast one calcium carbonate containing material is provided in form ofparticles having a specific surface area from 0.1 to 200 m²/g,preferably from 0.5 to 100 m²/g, more preferably from 1.0 to 50 m²/g,and most preferably from 2.0 to 10 m²/g, measured using nitrogen and theBET method according to ISO 9277:2010.

The at least one calcium carbonate containing material is suspended inwater, and thus, forms an aqueous suspension or slurry of calciumcarbonate containing material. According to one embodiment of thepresent invention, the aqueous suspension provided in process step a)has a solid content from 1 to 99 wt.-%, preferably from 15 to 70 wt.-%,more preferably from 10 to 50 wt.-%, and most preferably from 12 to 40wt.-%, based on the total weight of the suspension. The suspension ofprocess step a) can be provided undispersed or dispersed, i.e. thesuspension includes a dispersant.

According to a preferred embodiment, the suspension of step a) isundispersed, i.e. it does not contain a dispersant.

Step b)

In step b) of the process according to the present invention at leastone acid or acid salt is provided, wherein the anion of the acid or acidsalt is capable of forming water-insoluble calcium salts.

According to one embodiment of the present invention, the at least oneacid or acid salt is selected from the group consisting of strong acidshaving a pK_(a) value of less than or equal to 0 at 25° C., andmedium-strong acids having a pK_(a) value of between 0 and 8, inclusive,and weak acids having a pK_(a) value of between 8 and 20, inclusive, at25° C.

According to one embodiment of the present invention, the at least oneacid is selected from the group comprising citric acid, oxalic acid,phosphoric acid, sulfuric acid, arsenic acid, and iodic acid.

According to one embodiment of the present invention, the at least oneacid is an organic acid selected from the group comprising citric acidand oxalic acid. According to another embodiment of the inventiveprocess, the at least one acid is an inorganic acid selected from thegroup comprising phosphoric acid, sulfuric acid, arsenic acid and iodicacid.

According to yet another preferred embodiment of the present invention,the at least one acid is a non-polymeric acid that has a molecularweight of less than 1000 g/mol, preferably less than 750 g/mol, and morepreferably less than 500 g/mol.

According to another embodiment of the present invention, the at leastone acid is liquid at 25° C. and 1 bar. According to another embodimentof the present invention the at least one acid is solid at 25° C. and 1bar.

According to one embodiment of the present invention, the at least oneacid is dissolved in water. According to one embodiment of the presentinvention the solution of the at least one acid is a low concentratedsolution having a concentration of less than 0.1 M.

According to another embodiment of the present invention, the solutionof the at least one acid is a highly concentrated solution having aconcentration of more than 0.1 M. According to a preferred embodiment ofthe present invention the solution of the at least one acid has aconcentration of about 0.1 M.

An “acid salt” in the meaning of the present invention is defined as anH₃O⁺-ion provider that is at least partially neutralized by anon-hydrogen cation and, therefore, the “acid salt” comprises at leastone “acid anion” and at least one non-hydrogen cation.

According to one embodiment the non-hydrogen cation may possess onepositive charged, two positive charges or three positive charges.Cations possessing one positive charge are selected from the groupcomprising Na⁺, K⁺ and NH₄ ⁺, cations possessing two positive chargesare selected from the group comprising Mg²⁻ and Sr²⁺ and cationspossessing three positive charges are selected from the group comprisingAl³⁺ and Fe²⁺. Preferably the cation is a sodium cation.

According to one embodiment of the inventive process, said at least oneacid salt is selected from the group comprising sodium dihydrogencitrate, potassium dihydrogen citrate, disodium hydrogen citrate,dipotassium hydrogen citrate, trisodium citrate, tripotassium citrate,disodium oxalate, dipotassium oxalate, magnesium oxalate, sodiumhydrogen sulfate, sodium potassium sulfate, disodium sulfate,dipotassium sulfate, magnesium sulfate, sodium dihydrogen phosphate,potassium dihydrogen phosphate, disodium hydrogen phosphate, dipotassiumhydrogen phosphate, trisodium phosphate and tripotassium phosphate.

According to a preferred embodiment, the at least one acid salt istrisodium citrate.

According to one embodiment of the present invention the at least oneacid salt is provided in form of a solution. According to one embodimentof the present invention, the at least one acid salt is dissolved inwater. According to another embodiment of the present invention the atleast one acid salt is dissolved in an organic solvent, preferablyselected from the group comprising, methanol, ethanol, acetone, andmixtures thereof. If the acid salt is provided in form of a solution,the solution is preferably prepared in that the acid salt is added to asolvent, preferably water, having a temperature of at least 1° C.,preferably from 20° C. to 100° C., more preferably from 25° C. to 80° C.and most preferably from 30° C. to 60° C.

In one preferred embodiment, the acid salt is added to water at aboutroom temperature, i.e. at a temperature from 20° C.±2° C.

According to one embodiment of the present invention the solution of theat least one acid salt is a low concentrated solution having aconcentration of less than 0.1 M, preferably of less than 0.05 M, andmore preferably of less than 0.025 M. According to another embodiment ofthe present invention the solution of the at least one acid salt is ahighly concentrated solution having a concentration of more than 0.1 M,preferably of more than 0.2 M and more preferably of more than 0.5 M.According to a preferred embodiment of the present invention thesolution of the at least one acid salt has a concentration of about 0.1M.

According to an alternative embodiment, the acid salt is provided in dryform, e.g. in form of a dry powder.

According to one embodiment of the inventive process, the at least oneacid or acid salt is added in an amount from 0.001 to 40 wt.-%,preferably from 0.005 to 20 wt.-%, more preferably from 0.01 to 10 wt.-%and most preferably from 0.05 to 5 wt.-%, based on the total amount ofthe dry calcium carbonate containing material.

Step c)

In step c) of the process according to the present invention an anionicpolymeric binder is provided, wherein said binder comprises at least onemodified polysaccharide.

“Modified polysaccharides” in the meaning of the present invention arepolysaccharides, wherein at least a part of the hydroxyl groups iscarboxylated.

Additionally, the modified polysaccharides may contain othermodifications such as aldehyde groups.

Modified polysaccharides according to the present invention may comprisethe following structure:

wherein a part of the hydroxyl groups is carboxylated and “n” isindirectly represented by the intrinsic viscosity.

Polysaccharides are polymeric carbohydrate structures, formed ofrepeating units (at least 10) joined together by glycosidic bonds.Depending on the spatial arrangement of the glycosidic bonds, one maydistinguish between α- and β-glycosidic bonds. These structures may belinear, but may also contain various degrees of branching.Polysaccharides may also contain slight modifications of the repeatingunit. Exemplary polysaccharides are starch, cellulose, or glycogen, butalso structural polysaccharides such as cellulose and chitin.

According to one embodiment of the present invention, the at least onemodified polysaccharide has a degree of substitution of thehydroxyl-groups in the range from 0.4 to 2.0, preferably from 0.5 to1.8, more preferably from 0.6 to 1.6, and most preferably from 0.7 to1.5.

According to one embodiment of the present invention, the modifiedpolysaccharide is a carboxymethyl derivate and/or a carboxymethylhydroxypropyl derivate and/or a carboxymethyl hydroxyethyl derivate of apolysaccharide. For example, the modified polysaccharide can be acarboxymethylcellulose (CMC), an anionic starch, an anionic guar,xanthan gum, or mixtures thereof.

According to a preferred embodiment of the present invention, the atleast one modified polysaccharide is carboxymethylcellulose (CMC).

Carboxymethylcellulose (CMC) may be prepared from cellulose by reactionwith monochloroacetic acid in the presence of caustic soda to form thesodium salt of carboxymethylcellulose. Each repeating D-glycose unitcontains three hydroxyl groups capable of etherification, to give amaximum charge density of three carboxylic groups per monomer unit (i.e.a degree of substitution of three).

The molecular weight and the intrinsic viscosity of thecarboxymethylcellulose-based binder materials can be adjusted by anymethod that is known to the person skilled in the art, e.g., by additionof peroxides. Reference is made to DE 1 543 116 A1 describing a methodfor the preparation of low viscous, water-soluble CMC by oxidativedegradation with H₂O₂ and to DE 44 11 681 A1 describing the dependencyof the degradation of polysaccharide ether on the amount of oxidizingagent, temperature and duration of the treatment.

According to a preferred embodiment of the present invention, thecarboxymethylcellulose has an intrinsic viscosity in the range from 5 to500 ml/g, preferably from 10 to 450 ml/g, more preferably from 50 to 350ml/g and most preferably from 100 to 200 ml/g.

According to another preferred embodiment of the present invention, theat least one modified polysaccharide is an anionic starch.

The anionic starch is preferably chemically modified with anionic groupsselected from the group comprising carboxyl groups, carboxymethylgroups, carboxymethyl hydroxypropyl groups, carboxymethyl hydroxyethylgroups, phosphate groups, sulfonate groups and mixtures thereof. Theanionic starch can be chosen from amongst the chemically modifiedstarches originating from starches selected from the group comprisingwheat starch, corn starch, rice starch, potato starch, tapioca starch,maranta starch, sorghum starch and mixtures thereof. The anionic starchcan also be obtained from genetically modified sources comprisingamylopectin enriched starches. In one preferred embodiment, the anionicstarch is selected from those enriched in amylopectin, that is to saythe chemically modified starch is preferably selected from the groupconsisting of rice starch, potato starch, and mixtures thereof. Methodsfor preparing such anionic starches are known by the skilled person. Themolecular weight of the anionic starch can range from 1 000 to 1 000 000g/mol and is generally about 220 000 g/mol. The molecular weight of theanionic starch can be adjusted by the treatment with hydrogen peroxide(H₂O₂).

According to another preferred embodiment of the present invention, theat least one modified polysaccharide is an anionic guar.

Guar comprises a natural heteropolysaccharide (guaran) consisting ofgalactose units and mannose units usually in the ratio of 1:2 and is theendosperm component of guar seeds. In general, guar comprises a linearchain of 1,4-linked β-D-mannopyranosyl units with 1,6-linkedα-D-galactopyranosyl units. Guar seeds containing about 14 to 17 wt.-%husk, 35 to 42 wt.-% endosperm and 43 to 47 wt.-% embryo, are usuallydry-milled and screened to separate out the endosperm which is theindustrial guar of commerce. A guar derivative can be obtained, forexample, by modifying the heteropolysaccharide through the use ofenzymes, acids, oxidation media, temperature, radiation etc. Methods forpreparing such guar derivatives are known to the skilled person. Forexample, a modification may be obtained by the use of a commerciallyavailable α-D-galactosidase enzyme which is useful to removeα-D-galactopyranosyl units. By controlling the length of time that theguaran is exposed to the α-D-galactosidase enzyme, the extent of removalof α-D-galactopyranosyl units from the linear chain of mannose units canbe controlled. Additionally or alternatively, a modification of guar maybe obtained by etherification of guar with propyleneoxide orethyleneoxide resulting in a hydroxypropyl guar or hydroxyethyl guar.

According to one embodiment of the present invention, the anionic guaris a carboxymethyl guar (CMG) and/or a carboxymethyl hydroxypropyl guar(CMHEG) and/or a carboxymethyl hydroxyethyl guar (CMHEG). For example,carboxymethyl guar is obtained by reacting a guar with monochloroaceticacid in the presence of caustic soda.

According to one embodiment of the present invention, the anionicpolymeric binder of process step c) comprises one modifiedpolysaccharide. According to another embodiment of the presentinvention, the anionic binder of process step c) comprises two or moremodified polysaccharides. According to a preferred embodiment of thepresent invention, the anionic polymeric binder of process step c)consists of at least one modified polysaccharide. The anionic polymericbinder of process step c) may consist of one type of modifiedpolysaccharide, or may consist of a mixture of two or more types ofmodified polysaccharides.

According to one embodiment of the present invention, the anionicpolymeric binder employed in the process according to the presentinvention has a pH from 4.5 to 12, preferably from 7 to 11, and morepreferably from 8.0 to 10.5.

The anionic polymeric binder can be provided as solution or drymaterial. According to a preferred embodiment, the anionic polymericbinder is in form of an aqueous solution.

According to a preferred embodiment of the present invention, theanionic polymeric binder is in form of an aqueous solution having abinder concentration from 1 to 70 wt.-%, preferably from 2 to 55 wt.-%,more preferably from 5 to 50 wt.-%, and most preferably from 30 to 50wt.-%, based on the total weight of the solution.

The modified polysaccharide solution can be concentrated, for example,by ultrafiltration or thermal or drying. Dry modified polysaccharide ispreferably produced by thermal drying, more preferably by spray dryingand has a solids content of more than 90, preferably from 95 to 99.9wt.-%, based on the total weight of the modified polysaccharide.

According to one embodiment of the present invention the binder of stepc) is added in an amount from 0.001 to 20 wt.-%, preferably from 0.005to 15 wt.-%, more preferably from 0.01 to 10 wt.-%, and most preferablyfrom 0.05 to 5 wt.-%, based on the total weight of the dry calciumcarbonate containing material.

According to a preferred embodiment of the present invention, theanionic binder of step c) is at least one carboxymethylcellulose addedin an amount from 0.05 to 5 wt.-%, preferably from 0.1 to 2.5 wt.-%,based on the total weight of the dry calcium carbonate containingmaterial.

Step d)

In step d) of the process according to the present invention at leastone cationic polymer is provided.

The inventors of the present application surprisingly found that theaddition of at least one cationic polymer can lead to a better retentionof the self-binding pigment particles during paper production processes.Without being bound to any theory, it is believed that the anioniccharge of the anionic polymer binder is at least partially neutralizedby the cationic polymer.

The inventors also found that the addition of at least one cationicpolymer can reduce the amount of free polymer in the obtainedself-binding pigment particles suspension. Without being bound to anytheory, it is believed that the cationic polymer can improve theadhesion or adsorption of the anionic binder and/or the at least onecationic polymer on the ground calcium carbonate particles. This findingwas very surprising since it is known that the dispersion of groundcalcium carbonate with cationic starch can result in pigment particlesuspension containing high amounts of free polymer.

Furthermore, the inventors surprisingly found that the self-bindingproperties of the pigment particles are also improved. As a result,paper products comprising the inventive self-binding particles as fillermaterial exhibit an improved strength, and also allow the production ofpapers with high content of filler material. Another advantage is thatthe physical and optical properties of paper comprising the inventiveself-binding pigment particles as filler material are not impaired toany substantial degree.

According to one embodiment of the present invention, the at least onecationic polymer is selected from polyamines, polyethyleneimines,polyacrylamides, cationic epichlorohydrin resins,polydiallyldimethylammonium chloride, cationic starch, cationic guar, ormixtures thereof.

According to one embodiment of the present invention, the at least onecationic polymer is a polyamine, preferably a polyethyleneimine (PEI)being selected from the group comprising branched polyethyleneimines,linear polyethyleneimines and mixtures of the foregoing. Preferably, theratio of primary, secondary and tertiary amine functions in theinventive branched polyethyleneimines is in the range of 1:0.86:0.42 to1:1.20:0.76, prior to a possible modification of the branchedpolyethyleneimines.

According to one preferred embodiment of the present invention, the atleast one polyethyleneimine is selected from the group of modified andunmodified polyethyleneimines. Examples for suitable polyethyleneiminesare homopolymers of ethyleneimine (aziridine) or its higher homologuesand also the graft polymers of polyamidoamines or polyvinylamines withethyleneimine or its higher homologues. The polyethyleneimines can becrosslinked or uncrosslinked, quaternized and/or modified by reactionwith alkylene oxides, dialkyl or alkylene carbonates or C₁-C₈-carboxylicacids. The polyethyleneimines may be modified by reaction with alkyleneoxides such as ethylene oxide, propylene oxide or butylene oxide,dialkyl carbonates such as dimethyl carbonate and diethyl carbonate,alkylene carbonates such as ethylene carbonate or propylene carbonate,or C₁-C₈-carboxylic acids. Modified PEIs can include alkoxylatedpolyethyleneimines such as propoxylated polyethyleneimines (PPEIs) andethoxylated polyethyleneimines (EPEIs). Further preferred modifiedpolyethyleneimines can be obtained by reacting the unmodified PEIs withone or more C₁-C₂₈-fatty acids, preferably with one or more C₆-C₁₈-fattyacids and especially preferred with C₁₀-C₁₄-fatty acids, like, e.g.,coconut fatty acid.

The polyethyleneimine can have a weight average molecular weight M_(w)in the range of 1 000 g/mol and 1 000 000 g/mol. In another preferredembodiment of the present invention the polyethyleneimine is selectedfrom the group of linear polyethyleneimines having a weight averagemolecular weight M_(w) from 100 to 700 g/mol, and preferably from 146 to232 g/mol, and preferably is selected from triethylenetetramine,pentaethylenehexamine and tetraethylenepentamine. According to anotherpreferred embodiment the polyethyleneimine is selected from the group ofbranched polyethyleneimines having a weight average molecular weightM_(w) from 500 to 8 000 g/mol and preferably from 800 to 1 200 g/mol.

According to one embodiment of the present invention, the at least onecationic polymer is a cationic starch.

The cationic starch is preferably chemically modified with cationicgroups selected from the group comprising amino groups, immonium groups,ammonium groups, sulfonium groups, phosphonium groups, and mixturesthereof. The cationic starch can be chosen from amongst the chemicallymodified starches originating from virtual any natural sources providingfor starch in reasonable amounts. For example, the cationic starch canbe chosen from amongst the chemically modified starches originating fromstarches selected from the group comprising wheat starch, corn starch,rice starch, potato starch, tapioca starch, maranta starch, sorghumstarch and mixtures thereof. In one preferred embodiment, the cationicstarch is selected from those enriched in amylopectin, that is to saythe chemically modified starch is preferably selected from the groupconsisting of rice starch, potato starch, and mixtures thereof. Thecationic starch can also be obtained from genetically modified sourcescomprising amylopectin enriched starches. Methods for preparing suchcationic starches are known by the skilled person. The molecular weightof the cationic starch can range from 1 000 to 1 000 000 g/mol and isgenerally about 220 000 g/mol. The molecular weight of the cationicstarch can be adjusted by the treatment with hydrogen peroxide (H₂O₂).

According to another embodiment of the present invention, the at leastone cationic polymer is a cationic guar.

Guar comprises a natural heteropolysaccharide (guaran) consisting ofgalactose units and mannose units usually in the ratio of 1:2 and is theendosperm component of guar seeds. In general, guar comprises a linearchain of 1,4-linked β-D-mannopyranosyl units with 1,6-linkedα-D-galactopyranosyl units. Guar seeds containing about 14 to 17 wt.-%husk, 35 to 42 wt.-% endosperm and 43 to 47 wt.-% embryo, are usuallydry-milled and screened to separate out the endosperm which is theindustrial guar of commerce. A guar derivative can be obtained, forexample, by modifying the heteropolysaccharide through the use ofenzymes, acids, oxidation media, temperature, radiation etc. Methods forpreparing such guar derivatives are known to the skilled person. Forexample, a modification may be obtained by the use of a commerciallyavailable α-D-galactosidase enzyme which is useful to removeα-D-galactopyranosyl units. By controlling the length of time that theguaran is exposed to the α-D-galactosidase enzyme, the extent of removalof α-D-galactopyranosyl units from the linear chain of mannose units canbe controlled. A cationic guar can be obtained by reacting guar withderivatives of quaternary ammonium salts.

According to still another embodiment of the present invention, the atleast one cationic polymer is polydiallyldimethylammonium chloride(polyDADMAC).

PolyDADMAC (polydiallyldimethylammonium chloride) is a linearhomopolymer of diallyldimethylammonium chloride (DADMAC) having thefollowing structure:

The linear homopolymer formed from a monomer that has a quaternaryammonium and two unsaturated —CH═CH₂ functionalities is polymerized byfree-radical polymerization of the DADMAC. In the polyDADMAC structurequaternary ammonium groups are on rings that are included in thebackbone of the polymer chain. This composition means that thepolyDADMAC macromolecules tend to be quite stiff, having a longerpersistence length than, for instance, polyamines. For this reason,polyDADMAC is expected to have a more extended conformation in solution.The polyDADMAC can have a weight average molecular weight M_(w) in therange from 10 000 to 1 000 000 g/mol and preferably in the range from100 000 to 500 000 g/mol.

Further examples of cationic polymer that are suitable for the processof the present invention are polyacrylamides, or cationicepichlorohydrin resins.

According to an exemplary embodiment, the polyacrylamides includemonomers of dialkylaminoethyl(meth)acrylates,dialkylaminoethyl(meth)acrylamides, dialkylaminomethyl(meth)acrylamides,and dialkylamino-1,3-propyl(meth)acrylamides, preferably copolymerizedwith nonionic monomers, preferably arylamide.

According to another embodiment, the cationic epichlorohydrin resins arecopolymers comprising as the monomer one or more dicarboxylic acids andone or more monomers from the group of diamines, triamines,dialkanolamines or trialkanolamines and epichlorohydrin.

Preferably saturated or unsaturated, branched or unbranched C₂-C₁₀dicarboxylic acids, preferably C₃-C₉ dicarboxylic acids, C₄-C₈dicarboxylic acids, C₅-C₇ dicarboxylic acids, in particular adipic acidare used as the dicarboxylic acid monomers. Especially suitable as thesecond monomer of the binder polymer are linear and branched,substituted and unsubstituted diamines and triamines, in particularN-(2-aminoethyl)-1,2-ethanediamine. Preferably used dialkanolamines andtrialkanolamines include, for example, diethanolamine,N-alkyl-dialkanolamines such as N-methyl and N-ethyldiethanolamine andtriethanolamine. For monitoring and control of the molecular weightand/or the chain length, one or more monovalent amines such asmonoalkanolamines may be used during the polycondensation. Monoethanolis used preferably. The resulting intermediate product is reactedfurther with epichlorohydrin.

According to a preferred embodiment of the present invention, thecationic epichlorohydrin resin is a copolymer of adipic acid withN-(2-aminoethyl)-1,2-ethanediamine and epichlorohydrin.

According to one embodiment of the present invention, the at least onecationic polymer is a mixture of two or more of the aforementionedpolymers. According to another embodiment of the present invention, theat least one cationic polymer consists of one of the aforementionedpolymers.

According to one preferred embodiment, the at least one cationic polymeris polyDADMAC. According to another preferred embodiment, the at leastone cationic polymer is a cationic starch.

The at least one cationic polymer can be provided in an aqueous form,e.g., in the form of a water-based solution, or in form of an organicsolution, e.g., in an organic solvent selected from the group comprisingmethanol, ethanol, acetone, and mixtures thereof. However, the at leastone cationic polymer also may be provided in form of an emulsion or adispersion of water and/or organic solvents, or in form of a mixture ofa solution and/or an emulsion and/or a dispersion of water and/ororganic solvents.

If the at least one cationic polymer is provided in form of a solution,the solution is preferably prepared in that the at least one cationicpolymer is added to a solvent, preferably water, having a temperature ofat least 50° C., preferably from 50° C. to 100° C., more preferably from60° C. to 98° C. and most preferably from 70° C. to 96° C. For example,the solution is prepared in that the at least one cationic polymer isadded to water having a temperature of from 80° C. to 96° C., like from90° C. to 96° C. Alternatively, the solution is prepared in that the atleast one cationic polymer is added to a solvent, preferably water,having a temperature of below 50° C., preferably from 5° C. to 50° C.,more preferably from 10° C. to 40° C. and most preferably from 15° C. to30° C.

In one preferred embodiment, the cationic polymer solution is preparedin that the at least one cationic polymer is added to water at aboutroom temperature, i.e. at 20° C.±2° C.

According to an alternative embodiment, the at least one cationicpolymer is provided in dry form, e.g. in form of a dry powder.

In case the at least one cationic polymer is provided in the form of adispersion, the particle size of the cationic polymer can have a d₅₀value from 10 to 500 nm, preferably from 20 to 100 nm, and morepreferably from 25 to 80 nm.

The cationic polymer of step d) may be provided in form of a solution ordry material, preferably in form of a solution having a concentrationfrom 0.5 to 70 wt.-%, preferably from 1 to 25 wt.-%, more preferablyfrom 1.5 to 20 wt.-%, and most preferably from 2 to 10 wt.-%, based onthe total weight of the solution.

According to one embodiment of the present invention, the cationicpolymer is added in an amount such that the charge density of theobtained self-binding pigment particles is lower compared toself-binding pigment particles not containing the cationic polymer. Forexample, the cationic polymer can be added in an amount such that thecharge density of the obtained self-binding pigment particle is between−100 and −5 μEq/g, preferably between −80 and −10 μEq/g, and morepreferably between −70 and −15 μEq/g.

According to one embodiment of the present invention, the cationicpolymer of step d) is added in an amount from 0.001 to 20 wt.-%,preferably from 0.005 to 15 wt.-%, more preferably from 0.01 to 10wt.-%, and most preferably from 0.05 to 5 wt.-% or from 0.5 to 1.5wt.-%, based on the total weight of the dry calcium carbonate containingmaterial.

According to a preferred embodiment of the present invention, the atleast one cationic polymer of step d) is polyDADMAC, preferably added inan amount from 0.05 to 5 wt.-%, more preferably from 0.5 to 1.5 wt.-%,based on the total weight of the dry calcium carbonate containingmaterial of step a).

According to another preferred embodiment of the present invention, theat least one cationic polymer of step d) is cationic starch, preferablyadded in an amount from 0.05 to 5 wt.-%, more preferably from 0.5 to 1.5wt.-%, based on the total weight of the dry calcium carbonate containingmaterial of step a).

According to a preferred embodiment of the present invention, theanionic binder of step c) is at least one carboxymethylcellulose, andthe at least one cationic polymer of step d) is a cationic starch,wherein the binder is added in an amount from 0.01 to 20 wt.-%,preferably from 0.1 to 10 wt.-%, more preferably from 0.5 to 5 wt.-% andmost preferably from 0.1 to 2.5 wt.-%, based on the total weight of thedry calcium carbonate containing material.

According to an exemplary embodiment, the anionic binder of step c) is acarboxymethylcellulose, and the at least one cationic polymer of step d)is a cationic starch, wherein the binder is added in an amount of about0.5 wt.-%, and the cationic polymer is added in an amount of about 2.0wt.-%, based on the total weight of the dry calcium carbonate containingmaterial.

According to another exemplary embodiment, the calcium carbonatecontaining material is calcium carbonate, preferably precipitatedcalcium carbonate, the anionic binder of step c) is acarboxymethylcellulose, and the at least one cationic polymer of step d)is a cationic starch, wherein the binder is added in an amount of about0.5 wt.-%, and the cationic polymer is added in an amount of about 2.0wt.-%, based on the total weight of the dry calcium carbonate containingmaterial.

According to still another exemplary embodiment, the calcium carbonatecontaining material is calcium carbonate, preferably precipitatedcalcium carbonate, the at least one acid or acid salt of step b) istrisodium citrate, the anionic binder of step c) is acarboxymethylcellulose, and the at least one cationic polymer of step d)is a cationic starch, wherein the acid or acid salt is added in anamount of about 0.09 wt.-%, the binder is added in an amount of about0.5 wt.-%, and the cationic polymer is added in an amount of about 2.0wt.-%, based on the total weight of the dry calcium carbonate containingmaterial.

Step e)

In step e) of the process according to the present invention the aqueoussuspension of step a) is mixed with the at least one acid or acid saltof step b).

The inventors of the present invention surprisingly found that theaddition of an acid or acid salt to the aqueous suspension of step a)can improve the properties of the self-binding particles. For examplethe use of at least one acid or acid salt may lead to self-bindingpigment particles with improved properties. For example, suchself-binding pigment particles show an improved binding to the fibres inpaper when used as filler.

Without being bound to any theory it is believed that the improvedbinding to the fibres is based on the interaction boundaries between thecalcium carbonate containing pigment particles and the fibres.

The addition of an acid or acid salt to the aqueous suspension of stepa) modifies the surface of the calcium carbonate containing materialparticles, and can be especially advantageous for precipitated calciumcarbonate particles. PCC particles have many tips on their outer surfaceand, thus, are relatively rough. It is believed that these tips caninterlock with paper fibres during paper production processes, resultingin an improved binding between the particles and the fibres. However,the precipitated calcium carbonate particles can release Ca²⁺-ions fromthe inner particle core over time, and, therefore, decreased interactionboundaries between the pigment particles and fibres can be the result.

Surprisingly, the inventors have found that a way to overcome thisproblem is the treatment of the aqueous suspension of the calciumcarbonate containing material with acids or acid salts. Without beingbound to any theory, it is believed that during the treatment of theprecipitated calcium carbonate particles with acid or acid salt, waterinsoluble calcium-salts are formed, which may inhibit the release ofCa²⁺-ions from the precipitated calcium carbonate particles. As aresult, the binding between the precipitated calcium carbonate pigmentparticles and the fibres of the paper can be improved since the tips ofthe precipitated calcium carbonate pigment particles are no longer“degraded” or “dissolved” by the calcium release. This may allow interalia to increase the filler load in the paper while maintaining themechanical strength properties of the paper.

According to one embodiment of the inventive process, the at least oneacid or acid salt is added to the aqueous suspension of step a).According to another embodiment of the inventive process the aqueoussuspension of step a) is added to the at least one acid or acid salt.

According to one embodiment of the inventive process, the at least oneacid or acid salt is added in form of a suspension or solution to theaqueous suspension of step a). According to another embodiment of theinventive process, the at least one acid or acid salt is added in formof a solid to the aqueous suspension of step a). For example, the acidor acid salt can be added in form of a powder or granulate.

According to one embodiment of the inventive process the at least oneacid or acid salt and the aqueous suspension of step a) are mixed undershear. According to another embodiment of the inventive process theshear is agitated after mixing the acid or acid salt and the aqueoussuspension of step a). Shear is introduced, e.g., by stirring orshaking.

The mixing may be carried out under mixing and/or homogenizingconditions. The skilled person will adapt these mixing and/orhomogenizing conditions such as the mixing speed and temperatureaccording to his process equipment. For example, the mixing andhomogenizing may take place by means of a ploughshare mixer. Ploughsharemixers function by the principle of a fluidized bed producedmechanically. Ploughshare blades rotate close to the inside wall of ahorizontal cylindrical drum and convey the components of the mixture outof the product bed and into the open mixing space. The fluidized bedproduced mechanically ensures intense mixing of even large batches in avery short time. Choppers and/or dispersers are used to disperse lumpsin a dry operation. Equipment that may be used in the inventive processis available, for example, from Gebruder Lodige Maschinenbau GmbH,Germany or from Silverson (U.S.A.). Furthermore, a tubular mixingapparatus, for example, from Ystral GmbH, Ballrechten-Dottingen, Germanymay be used. Another equipment type that may be used in the inventiveprocess is a MEGATRON® Inline homogenizer from Kinematika AG,Switzerland.

According to one embodiment of the present invention, process step e) iscarried out using a fluidized bed mixer or ploughshare mixer.

The process step e) may be carried out at room temperature, i.e. at 20°C.±2° C., or at other temperatures. According to one embodiment theprocess step e) is carried out at a temperature from 5 to 140° C.,preferably from 10 to 110° C., and most preferably from 20 to 105° C.Heat may be introduced by internal shear or by an external source or acombination thereof.

According to an exemplary embodiment of the invention, the suspension ofstep a) and/or the at least one acid or acid salt of step b) ispreheated before these components are mixed in process step e).

According to one embodiment of the present invention, process step e) iscarried out for at least 1 s, preferably for at least 1 min, e.g., forat least 15 min, 30 min, 1 hour, 2 hours, 4 hours, 6 hours, 8 hours, or10 hours.

According to one embodiment of the inventive process the suspensionobtained in step e) is used without any further treatment in step f).According to another embodiment of the inventive process the suspensionobtained in step e) is up-concentrated before step f).

The solids content of the suspension can be adjusted by the methodsknown to the skilled person. To adjust the solids content of thesuspension obtained in step e), the suspension may be partially or fullydewatered by a filtration, centrifugation or thermal separation process.For example, the suspensions may be partially or fully dewatered by afiltration process such as nanofiltration or a thermal separationprocess such as an evaporation process. Alternatively, water may beadded to the suspension (e.g. resulting from filtration) until thedesired solids content is obtained. Additionally or alternatively, aself-binding pigment particle suspension having an appropriate lowercontent of solid particles may be added to the particulate material ofthe mixed suspension until the desired solid content is obtained.

According to one embodiment of the inventive process the suspensionobtained by step e) has a solid content from 2 to 99 wt.-%, preferablyfrom 10 to 60 wt.-%, more preferably from 15 to 45 wt.-%, and mostpreferably from 20 to 30 wt.-%, based on the total weight of thesuspension.

Step f)

In step f) of the process according to the present invention the aqueoussuspension obtained by step e) is mixed with the anionic polymericbinder of step c) and the at least one cationic polymer of step d).

According to another embodiment of the inventive process the suspensionobtained in step e) is up-concentrated before step f). Theup-concentration can be carried out by using thermal and/or mechanicalmethods well known to the skilled person.

According to one embodiment of the inventive process the suspensionobtained by step e) is, in a first step, mixed with the anionicpolymeric binder of step c), and then, in a second step, is mixed withthe at least one cationic polymer of step d).

According to one embodiment of the inventive process the suspensionobtained by step e) is, in a first step, mixed with the at least onecationic polymer of step d), and then, in a second step, is mixed withthe anionic polymeric binder of step c).

According to another embodiment of the inventive process the suspensionobtained by step e) is mixed with the anionic polymeric binder of stepc) and the at least one cationic polymer of step d) in one step.

According to one exemplary embodiment of the present invention, in afirst step, the suspension obtained by step e) is mixed with the anionicpolymeric binder of step c), wherein said binder is provided in form ofa solution, and then, in a second step, the at least one cationicpolymer of step d) is added to the suspension in form of a dry powder.

According to another exemplary embodiment of the present invention, in afirst step, the at least one cationic polymer of step d) is mixed withthe anionic polymeric binder of step c) to form a premixed solution,wherein the cationic polymer and the binder are provided in form of asolution, and then, in a second step, the premixed solution is mixedwith the suspension obtained by step e).

According to another exemplary embodiment of the present invention, in afirst step, the suspension obtained by step e) is mixed with the anionicpolymeric binder of step c), and then, in a second step, the mixedsuspension is added to the at least one cationic polymer of step d),wherein the cationic polymer is in form of a solution. The solution ofthe cationic polymer may also contain pulp fibres to be used inpapermaking processes. According to one embodiment of the presentinvention, the self-binding pigment particles are produced in situduring a paper making process, wherein, in a first step, the suspensionobtained by step e) is mixed with the anionic polymeric binder of stepc), and then, in a second step, the mixed suspension is added to thecationic polymer of step d), wherein the at least one cationic polymeris in form of a suspension containing pulp fibres.

The mixing step f) may be carried out under mixing and/or homogenizingconditions. The skilled person will adapt these mixing and/orhomogenizing conditions such as the mixing speed and temperatureaccording to his process equipment. For example, the mixing andhomogenizing may take place by means of a ploughshare mixer. Ploughsharemixers function by the principle of a fluidized bed producedmechanically. Ploughshare blades rotate close to the inside wall of ahorizontal cylindrical drum and convey the components of the mixture outof the product bed and into the open mixing space. The fluidized bedproduced mechanically ensures intense mixing of even large batches in avery short time. Choppers and/or dispersers are used to disperse lumpsin a dry operation. Equipment that may be used in the inventive processis available, for example, from Gebruder Lodige Maschinenbau GmbH,Germany or from Silverson (U.S.A.). Furthermore, a tubular mixingapparatus, for example, from Ystral GmbH, Ballrechten-Dottingen, Germanymay be used. Another equipment type that may be used in the inventiveprocess is a MEGATRON® Inline homogenizer from Kinematika AG,Switzerland.

According to one embodiment of the present invention, process step f) iscarried out using a fluidized bed mixer or ploughshare mixer.

The process step f) may be carried out at room temperature, i.e. at 20°C.±2° C., or at other temperatures. According to one embodiment theprocess step f) is carried out at a temperature from 5 to 140° C.,preferably from 10 to 110° C., and most preferably from 20 to 105° C.Heat may be introduced by internal shear or by an external source or acombination thereof.

According to an exemplary embodiment of the invention, the suspensionobtained by step e) and/or the anionic polymeric binder of step c)and/or the at least one cationic polymer of step d) are mixed in processstep f) and afterwards are heated to a temperature from 50 to 120° C.,or from 60 to 110° C., or preferably from 70 to 105° C. for about 30minutes, or preferably for about 60 minutes.

According to one embodiment of the present invention, process step f) iscarried out for at least 1 s, preferably for at least 1 min, e.g., forat least 15 min, 30 min, 1 hour, 2 hours, 4 hours, 6 hours, 8 hours, or10 hours.

To ensure a better dispersion, a dispersant may also be added to any ofthe components used in the inventive process, e.g., in the form of anaqueous solution and/or a powder of a dispersant. A suitable dispersantis preferably selected from the group comprising homopolymers orcopolymers of polycarboxylic acid salts based on, for example, acrylicacid, methacrylic acid, maleic acid, fumaric acid or itaconic acid andacrylamide or mixtures thereof. Homopolymers or copolymers of acrylicacid are especially preferred. The weight average molecular weight M_(w)of such products is preferably in the range from 2 000 to 15 000 g/mol,with a weight average molecular weight M_(w) from 3 000 to 7 000 g/molor 3 500 to 6 000 g/mol being especially preferred. According to anexemplary embodiment, the dispersant is sodium polyacrylate having aweight average molecular weight M_(w) from 2 000 to 15 000 g/mol,preferably from 3 000 to 7 000 g/mol, and most preferably from 3 500 to6 000 g/mol.

According to a preferred embodiment, no dispersant is added in processstep f).

The mixing step may be carried out at a high solid content, i.e. at asolid content from 50 to 80 wt.-%, based on the total weight of thesuspension. However, the mixing step can be carried out at a solidcontent of more than 80 wt.-%, based on the total weight of thesuspension, e.g. by using a ploughshare mixer.

The solids content of the suspension can be adjusted by the methodsknown to the skilled person. To adjust the solids content of an aqueoussuspension, the suspension may be partially or fully dewatered by afiltration, centrifugation or thermal separation process. For example,the suspensions may be partially or fully dewatered by a filtrationprocess such as nanofiltration or a thermal separation process such asan evaporation process. Alternatively, water may be added to the solidmaterial (e.g. resulting from filtration) until the desired solidscontent is obtained. Additionally or alternatively, a self-bindingpigment particle suspension or other pigment particle suspension havingan appropriate lower content of solid particles may be added to theparticulate material of the mixed suspension until the desired solidcontent is obtained. The additionally added self-binding pigmentparticle suspension or other pigment particles suspensions can bedispersed or undispersed.

According to one embodiment of the present invention, the solids contentof the mixed suspension of step f) is adjusted so that it is from 10 to80 wt.-%, more preferably from 20 to 70 wt.-%, most preferably from 40to 65 wt.-%, based on the total weight of the suspension.

According to a preferred embodiment of the present invention, the solidcontent of the mixed suspension of step f) is adjusted to a high solidcontent so that it is from 50 to 80 wt.-%, more preferably from 60 to 79wt.-%, most preferably from 65 to 78 wt.-%, based on the total weight ofthe suspension.

Further, Optional Process Steps

According to an optional embodiment of the present invention, theprocess further comprises a step of concentrating the suspension ofself-binding pigment particles obtained by the process of the presentinvention.

The solids content of the obtained self-binding pigment particlesuspension can be adjusted by concentrating methods known to the skilledperson. The concentrating of the corresponding pigment materialsuspension may be achieved by means of a thermal process, for example inan evaporator, or by means of a mechanical process, for example in afilter press such as nanofiltration, and/or centrifuge.

The solid content of the self-binding pigment particle suspensionobtained by the process of the present invention can be concentrated sothat it is from 10 to 80 wt.-%, more preferably from 20 to 70 wt.-%,most preferably from 40 to 60 wt.-%, based on the total weight of thesuspension. According to one preferred embodiment, the solid content ofthe obtained self-binding pigment particle suspension is concentrated toa medium solid content so that it is from 50 to 60 wt.-%. Alternatively,the solid content of the obtained self-binding pigment particlesuspension can be concentrated to a high solid content so that it isfrom 50 to 80 wt.-%, more preferably from 60 to 79 wt.-%, mostpreferably from 65 to 78 wt.-%, based on the total weight of thesuspension.

According to one optional embodiment of the present invention, the stepof concentrating the self-binding particle suspension obtained by theprocess of the present invention is carried out such that a dry productis obtained. The term “dry product” is understood to refer to pigmentparticles having a total surface moisture content of less than 0.5wt.-%, preferably less than 0.2 wt.-% and more preferably less than 0.1wt.-%, based on the total weight of the pigment particles.

If the inventive process further comprises the optional step ofconcentrating the obtained self-binding pigment particle suspension suchthat a dry product or a suspension having a solids content of at least65 wt.-%, more preferably at least 80 wt.-% and most preferably at least90 wt.-%, based on the total weight of the self-binding pigment particlesuspension, is obtained, the dry product or the suspension may berediluted. If the dry product or the suspension is rediluted, the solidscontent in the obtained suspension is adjusted such that it is at least1 wt.-%, preferably from 1 wt.-% to 80 wt.-%, more preferably from 5wt.-% to 60 wt.-%, even more preferably from 10 wt.-% to 50 wt.-%, andmost preferably from 15 wt.-% to 45 wt.-%, based on the total weight ofthe self-binding pigment particle suspension.

In one preferred embodiment of the present invention, the process of thepresent invention may lead directly to high solids suspension ofself-binding pigment particles, i.e. to a suspension having a solidcontent from 50 to 80 wt.-%, based on the total weight of theself-binding pigment particle suspension, which means that an additionalconcentration step is not implemented in the process of the presentinvention.

The Self-Binding Pigment Particle Suspension

According to a further aspect, the present invention provides aself-binding pigment particle suspension which is obtainable by theprocess according to the present invention.

The inventive self-binding pigment particles can have a specific surfacearea of from 0.1 to 200 m²/g, preferably from 1 to 25 m²/g, morepreferably from 2 to 15 m²/g, and most preferably from 3 to 12 m²/g,measured using nitrogen and the BET method according to ISO 9277:2010.

According to a further aspect of the present invention, the self-bindingpigment particle suspension obtainable by the inventive process is usedin paper, plastics, paint, coatings, concrete and/or agricultureapplications. For example, the inventive particle suspension can beemployed as filler material in these applications.

According to an exemplary embodiment of the present invention, theself-binding particle suspension obtainable by the inventive process isused in paper, e.g., in wet end process of a paper machine, preferablyin cigarette paper, board and/or coating applications, or preferably assupport for rotogravure and/or offset and/or ink jet printing and/orcontinuous ink jet printing and/or flexography and/or electrophotographyand/or decoration surfaces.

Another application is the coating of tree leaves and/or plant leaves toreduce sun light and UV exposure of the leaf surface.

According to a further aspect of the present invention, a paper productcomprising the inventive self-binding pigment particles is provided,wherein the pigment particles comprise calcium carbonate containingmaterial particles which are at least partially coated with anwater-insoluble calcium salt formed from an acid or acid salt, ananionic polymeric binder comprising at least one modifiedpolysaccharide, and at least one cationic polymer.

According to one embodiment the paper comprising the inventiveself-binding pigment particles has a higher tensile index compared to apaper product, wherein the inventive self-binding pigment particles arereplaced by the same amount of calcium carbonate containing materialparticles. According to one embodiment of the present invention,preferably the tensile index is at least 5% higher, more preferably atleast 7% higher, and most preferably at least 10% higher compared to thetensile index of a paper product, wherein the inventive self-bindingpigment particles are replaced by the same amount of calcium carbonatecontaining material particles, and wherein the tensile index wasdetermined according to ISO 1924-2:2008. In a preferred embodiment theinventive self-binding pigment particles as filler material have atensile index of at least 20 Nm/g, preferably at least 22 Nm/g at afiller loading of 20 wt.-%, based on the total weight of the paperproduct.

It is to be understood that the advantageous embodiments described abovewith respect to the inventive method for making self-binding pigmentparticles also can be used for preparing or defining the inventivesuspension and its use. In other words, the preferred embodimentsdescribed above and any combinations of these embodiments can also beapplied to the inventive suspension and its use.

The scope and interest of the invention will be better understood basedon the following figures and examples which are intended to illustratecertain embodiments of the invention and are non-limitative.

DESCRIPTION OF THE FIGURES

FIG. 1 shows a diagram wherein the breaking length of the testedhandsheets is plotted against the filler content.

FIG. 2 shows a diagram wherein the tensile index of the testedhandsheets is plotted against the filler content.

FIG. 3 shows a diagram wherein the tensile energy adsorption of thetested handsheets is plotted against the filler content.

FIG. 4 shows a diagram wherein the Scott bond, also referred to asinternal bond in z-direction of the tested handsheets is plotted againstthe filler content.

EXAMPLES 1. Measurement Methods

In the following, materials and measurement methods implemented in theexamples are described.

BET Surface Area

The specific surface area was measured via the BET (Brunauer, St.,Emmett, P. H., Teller, E. (1938): Adsorption of Gases in MultimolecularLayers, J. Am. Chem. Soc., 60, 309.) method according to ISO 9277:2010using nitrogen, following conditioning of the sample by heating at 250°C. for a period of 30 minutes. Prior to such measurements, the samplewas filtered within a Büchner funnel, rinsed with deionised water anddried overnight at 90 to 100° C. in an oven. Subsequently the dry cakewas ground thoroughly in a mortar and the resulting powder placed in amoisture balance at 130° C. until a constant weight is reached.

Particle Size

The particle distribution of the calcium carbonate containing materialparticles was measured using a Sedigraph 5120 from the companyMicromeritics, USA. The method and the instrument are known to theskilled person and are commonly used to determine grain size of fillersand pigments. The measurement was carried out in an aqueous solutioncomprising 0.1 wt.-% Na₄P₂O₇. The samples were dispersed using a highspeed stirrer and supersonics.

Solids Content of an Aqueous Suspension

The suspension solids content (also known as “dry weight”) wasdetermined using a Moisture Analyser HR73 from the companyMettler-Toledo, Switzerland, with the following settings: temperature of120° C., automatic switch off 3, standard drying, 5 to 20 g ofsuspension.

Intrinsic Viscosity

The intrinsic viscosity was determined by a Schott AVS 370 system. Thesamples were dissolved in a 0.2 M NaCl solution, and subsequently, thepH was adjusted to 10 with NaOH. Measurements were performed at 25° C.with a capillary type Oa and corrected using the Hagenbach correction.

Degree of Carboxylation

The degree of carboxylation was determined by conductometric titrationaccording to Katz et al. “The determination of strong and weak acidicgroups in sulfite pulps” (Svensk Paperstidn., 1984, 6, pp. 48-53).

2. Examples Example 1 Comparative Example

A precipitated scalenohedral calcium carbonate (S-PCC) (commerciallyavailable as slurry with a solid content of 13 wt.-% from Omya,Switzerland) having a fineness corresponding to a d₅₀ value of 2.5 μm, ad₉₅ of 5 μm, a d₃₀ of 2 μm and a specific surface area of 3.4 m² g⁻¹ wasemployed as calcium carbonate containing material.

Example 2 Comparative Example

A precipitated scalenohedral calcium carbonate (S-PCC) (commerciallyavailable as slurry with a solid content of 13 wt.-% from Omya,Switzerland) having a fineness corresponding to a d₅₀ value of 2.5 μm, ad₉₅ of 5 μm, a d₃₀ of 2 μm and a specific surface area of 3.4 m² g⁻¹ wasemployed as calcium carbonate containing material. Trisodium citrate(commercially available from Sigma Aldrich) was employed as acid, andtwo different carboxymethylcelluloses (CMC) (commercially available fromMare Austria GmbH) having a molecular weight of 60 000 g/mol (NiklacellT10G) and of 200 000 g/mol (Niklacell CH90F) were employed as anionicbinder. The intrinsic viscosity of the CMCs was 168 ml/g (NiklacellT10G) and 298 ml/g (Niklacell CH90F), and the degree of substitution was0.8 for both.

The PCC was used in the form of a suspension having a solids content of13 wt.-%. 0.09 wt.-% trisodium citrate, based on the total amount of thedry PCC, was added to said slurry in a first step and, afterwards, 0.2wt.-% Niklacell T10G and 0.28 wt.-% Niklacell CH90F, based on the totalamount of the dry PCC, were added to said slurry in a second step,wherein the sodium citrate was added in form of a solution in waterhaving a concentration of 35 wt.-% sodium citrate, based on the totalweight of the solution, and the CMC was added in form of an aqueoussolution containing 6 wt.-% CMC, based on the total amount of thesolution.

Example 3 Inventive Example

2 wt.-% cationic starch (C*Bond HR 35845, commercially available fromCargill Deutschland GmbH, Germany), based on the total amount of the dryPCC, was added as cationic polymer to the suspension obtained in Example2 in form of a powder and, afterwards, the suspension was heated to 100°C. and stirred for 60 min. During the treatment, the solid content waskept at 50 wt.-%, based on the total weight of the suspension. Thesuspension was cooled to room temperature.

Example 4 Inventive Example

2 wt.-% cationic starch (C*Bond HR 35845, commercially available fromCargill Deutschland GmbH, Germany), based on the total amount of dry PCCin the fibrous suspension, was added to a fibre suspension of Eucalyptuspulp (Jarilyptus) and, afterwards, the suspension obtained in Example 2was added. The starch was prepared by cooking the starch at 100° C. inwater having a concentration of 1.5 wt.-%, based on total weight of thesuspension. Sheets were formed and tested as described below.

Testing of Mechanical Strength Properties of Wood Free, Uncoated Papercontaining the Surface-Modified Precipitated Calcium Carbonate Particlesof Example 3 and 4 as Filler

Eucalyptus pulp (Jarilyptus) refined to 30° SR was used as pulp. Thesurface modified precipitated calcium carbonate particles of Examples 3and 4 were used as fillers. In addition, a precipitated scalenohedralcalcium carbonate (S-PCC) (commercially available as slurry with a solidcontent of 13 wt.-% from Omya, Switzerland) was employed having afineness corresponding to a d₅₀ value of 2.5 μm, a d₉₅ of 5 μm, a d₃₀ of2 μm and a specific surface area of 3.4 m² g⁻¹ and Examples 1 and 2 wereused as Comparative Examples. The fillers were diluted with water to aconcentration of 10 wt.-%, based on the total amount of the suspension,and deagglomerated with a high speed stirrer (Kinematica, Switzerland).

60 g (dry) pulp were diluted in 10 dm³ tap water, and then the filler tobe tested was added in an amount so as to obtain the overall fillercontent based on the final paper weight. The suspension was stirred for30 minutes. Subsequently, 0.06% (based on dry weight) of apolyacrylamide (Polymin 1530, commercially available from BASF,Ludwigshafen, Germany) was added as a retention aid and sheets of 78g/m² were formed using the Rapid-Kothen hand sheet former. Each sheetwas dried using the Rapid-Kothen drier.

The filler content in the handsheets was determined by burning a quarterof a dry handsheet in a muffle furnace heated to 570° C. After theburning was completed, the residue was transferred in a desiccator andallowed to cool down. When room temperature was reached, the weight ofthe residue was measured and the mass was related to the initiallymeasured weight of the dry quarter hand sheet. The filler content in theexamples was 18% to 32%.

The mechanical strength properties of the handsheets were characterizedafter drying of the handsheets by the breaking length according to ISO1924-2:2008, the tensile index according to ISO 1924-2:2008, the tensileenergy absorption according to ISO 1924-2:2008, and the internal bond(z-direction), also referred to as scott bond, according toSCAN-P80:98/TAPPI T541.

FIGS. 1 to 4 show the mechanical properties of the tested handsheets.The data show that the use of the surface-modified particles of thepresent invention allows an increase in the filler load from about 20%to about 27% i.e. by about 7% without affecting the mechanical strengthproperties of the paper. In the case of the internal bond (FIG. 4), theeffect is even stronger, such that even higher filler contents would bepossible.

1. A self-binding pigment particle suspension obtained by the processcomprising the following steps: a) providing an aqueous suspensioncomprising at least one calcium carbonate containing material, b)providing at least one acid or acid salt in an amount from 0.001 to 40wt.-% based on the total weight of the dry calcium carbonate containingmaterial, wherein the anion of the acid or acid salt is capable offorming water-insoluble calcium salts, and wherein the at least one acidor acid salt of step b) is an acid salt comprising at least onenon-hydrogen cation selected from the group consisting of Na⁺, K⁺, NH₄⁺, Mg²⁺, Sr²⁻ and Fe²⁺, c) providing an anionic polymeric binder in anamount from 0.001 to 20 wt.-% based on the total weight of the drycalcium carbonate containing material, wherein the binder comprises atleast one modified polysaccharide, d) providing at least one cationicpolymer in an amount from 0.001 to 20 wt.-% based on the total weight ofthe dry calcium carbonate containing material, e) mixing the aqueoussuspension of step a) with the at least one acid or acid salt of step b)to obtain a suspension of calcium carbonate containing material that isat least partially coated with a water-insoluble calcium salt formedfrom the anion of the acid or the acid salt, and f) mixing thesuspension of step e), the anionic polymeric binder of step c) and theat least one cationic polymer of step d) to obtain an aqueous suspensionof self-binding pigment particles, wherein the self-binding pigmentparticles so obtained comprise calcium carbonate containing materialwhich is at least partially coated with a water-insoluble calcium saltformed from the anion of the acid or acid salt, the anionic bindercomprising the at least one modified polysaccharide, and the at leastone cationic polymer.
 2. The suspension of claim 1, wherein in step f)the suspension obtained by step e) is, in a first step, mixed with theanionic polymeric binder of step c), and then, in a second step, ismixed with the at least one cationic polymer of step d).
 3. Thesuspension of claim 1, wherein in step f) the suspension obtained bystep e) is mixed with the anionic polymeric binder of step c) and the atleast one cationic polymer of step d) in one step.
 4. The suspension ofclaim 1, wherein in step f) the suspension obtained by step e) is, in afirst step, mixed with the at least one cationic polymer of step d), andthen, in a second step, is mixed with the anionic polymeric binder ofstep c).
 5. The suspension of claim 1, wherein the suspension obtainedby step e) is concentrated before step f).
 6. The suspension of claim 1,wherein the at least one calcium carbonate containing material isselected from the group consisting of calcium carbonate, calciumcarbonate containing minerals, mixed calcium carbonate based fillers,and any mixture thereof.
 7. The suspension of claim 1, wherein the atleast one calcium carbonate containing material is precipitated calciumcarbonate (PCC).
 8. The suspension of claim 7, wherein the PCC isscalenohedral PCC (S-PCC), rhombohedral PCC (R-PCC), prismatic PCC(P-PCC), cubic PCC (C-PCC), or any mixture thereof.
 9. The suspension ofclaim 1, wherein the at least one calcium carbonate containing materialof step a) is provided in form of particles having a weight medianparticle diameter d₅₀ value from 0.1 to 100 μm.
 10. The suspension ofclaim 1, wherein the at least one calcium carbonate containing materialof step a) is provided in form of particles having a specific surfacearea from 0.1 to 200 m²/g.
 11. The suspension of claim 1, wherein theaqueous suspension of step a) has a solid content from 10 to 70 wt.-%,based on the total weight of the suspension.
 12. The suspension of claim1, wherein the suspension of step a) further comprises talc, kaolin,TiO₂, bentonite or any mixture thereof.
 13. The suspension of claim 1,wherein the at least one acid or acid salt of step b) is added in anamount from 0.005 to 20 wt.-%, based on the total weight of the drycalcium carbonate containing material.
 14. The suspension of claim 1,wherein the at least one acid or acid salt of step b) is selected fromthe group consisting of citric acid, oxalic acid, phosphoric acid,sulphuric acid, arsenic acid, iodic acid, acid salts thereof, and anymixture thereof.
 15. The suspension of claim 1, wherein the at least oneacid or acid salt of step b) is an acid salt comprising at least onenon-hydrogen cation that is sodium.
 16. The suspension of claim 1,wherein the at least one acid or acid salt of step b) is an acid saltselected from the group consisting of sodium dihydrogen citrate,potassium dihydrogen citrate, disodium hydrogen citrate, dipotassiumhydrogen citrate, trisodium citrate, tripotassium citrate, disodiumoxalate, dipotassium oxalate, magnesium oxalate, sodium hydrogensulfate, sodium potassium sulfate, disodium sulfate, dipotassiumsulfate, magnesium sulfate, sodium dihydrogen phosphate, potassiumdihydrogen phosphate, disodium hydrogen phosphate, dipotassium hydrogenphosphate, trisodium phosphate and tripotassium phosphate.
 17. Thesuspension of claim 1, wherein the at least one acid or acid salt ofstep b) is trisodium citrate.
 18. The suspension of claim 1, wherein thesuspension obtained by step e) has a solid content from 2 to 60 wt.-%,based on the total weight of the suspension.
 19. The suspension of claim1, wherein the at least one modified polysaccharide is a carboxymethylderivate, a carboxymethyl hydroxypropyl derivate, a carboxymethylhydroxyethyl derivate of a polysaccharide, a carboxymethylcellulose, ananionic guar, an anionic starch, xanthan gum, or any mixture thereof.20. The suspension of claim 1, wherein the at least one modifiedpolysaccharide has a degree of substitution of the hydroxyl groups inthe range from 0.4 to 2.0.
 21. The suspension of claim 1, wherein the atleast one modified polysaccharide has a degree of substitution of thehydroxyl groups in the range from 0.7 to 1.5.
 22. The product of claim1, wherein the intrinsic viscosity of the at least one modifiedpolysaccharide is in the range from 5 to 500 ml/g.
 23. The product ofclaim 1, wherein the binder of step c) is in form of an aqueous solutionor dry material.
 24. The suspension of claim 1, wherein the binder ofstep c) is in form of an aqueous solution having a binder concentrationfrom 1 to 70 wt.-%, based on the total weight of the solution.
 25. Thesuspension of claim 1, wherein the binder of step c) is added in anamount from 0.005 to 15 wt.-%, based on the total weight of the drycalcium carbonate containing material.
 26. The suspension of claim 1,wherein the at least one cationic polymer of step d) is selected fromthe group consisting of polyethyleneimines, polyacrylamides, cationicepichlorohydrin resins, cationic starch, cationic guar, and any mixturethereof.
 27. The suspension of claim 1, wherein the at least onecationic polymer of step d) is in form of a solution or dry material.28. The suspension of claim 1, wherein the at least one cationic polymerof step d) is in form of a solution having a concentration from 0.5 to70 wt.-%, based on the total weight of the solution.
 29. The suspensionof claim 1, wherein the at least one cationic polymer of step d) isadded in an amount from 0.005 to 15 wt.-%, based on the total weight ofthe dry calcium carbonate containing material.
 30. A product comprisingthe suspension of claim 1, a concentrated suspension thereof, orself-binding particles obtained from drying the suspension.
 31. Paper,paint, plastic, coating, concrete or agriculture product comprising theproduct of claim
 30. 32. A paper product comprising self-binding pigmentparticles, wherein the pigment particles comprise calcium carbonatecontaining material which is at least partially coated with awater-insoluble calcium salt formed from an anion of an acid or acidsalt, an anionic binder comprising at least one modified polysaccharide,and at least one cationic polymer.